Bis-pyrazolone for color photography



United States Patent Office BIS-PYRAZOLONE FOR COLOR PHOTOGRAPHY George W. Sawdey, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application December 15, 1951, Serial No. 261,909

Claims. (Cl. 95-6) This invention relates to the preparation and use of unsymmetrical bis-pyrazolone coupler compounds in color photography.

In systems of color photography utilizing coupler compounds in photographic emulsion layers or in color-forming developing solutions, it is sometimes desirable to employ two couplers of similar nature, magenta couplers, for example, giving dyes having absorption maxima at different wave lengths. This may be for the purpose of securing a broader absorption range or of shifting the maximum of absorption of the final dye to a point which cannot be obtained by other means. In the past this has been accomplished either by coating a physical mixture of two couplers in the same emulsion layer or by coating each coupler in a separate layer, the one layer being superimposed on the other. Both of these methods have serious disadvantages. In the first, for example, unless the two components have exactly the same reactivity toward the oxidation product of the color developer, then one of the dyes will predominate and the resulting dye will not be a truly proportional mixture. In the second method, the above objection is also pertinent although in this case it is easier to compensate for it. However, this technique requires an extra coating operation.

I have discovered that the desired result may be achieved and the disadvantages of the mentioned methods avoided by the use as couplers of the reaction prod- & 3 3

2,706,683 Patented Apr. 19, 1955 4-methoxy-, 4-nitro-, and 4-hydroxy groups. A and D may, for example, be hydrogen, alkyl, aryl or substituted aryl amino or acylamino and B and C may, for example, be hydrogen, alkyl, aryl or substituted aryl groups. However, the pairs of groups AD and BC are chosen in such a way that if AD are the same, then BC are dissimilar and vice versa. Thus, the compounds of the invention have the above general formula in which at least two of the substituents A, B, C and D are dilferent.

The unsymmetrical bis-pyrazolone compounds having the above structure are particularly advantageous since during the process of color development in which silver halide is reduced to silver by means of a primary aromatic amino developing agent, the bis-pyrazolones split at the moment of coupling to yield two fragments which react with the developer oxidation product at approximately equivalent rates. This is surprising since the prior art teaches that when symmetrical 4,4 bis-pyrazolones react with color developers, only one of the pyrazolone nuclei reacts with the color developer. Accordingly, in those cases where it is desirable to obtain the effects of two difierent pyrazolone couplers, I can dispense with having to prepare two pyrazolone couplers of high purity and having to weigh these out separately; instead, there can be used a single pure compound in the required quantity. Moreover, the two pyrazolone nuclei obtained from the unsymmetrical bis-pyrazolone compounds appear to produce approximately the same quantity of dye with a given color developing agent and consideration need not be given to differences in reactivity of pyrazolones which are present when the discrete pyrazolone couplers are used.

Particularly valuable unsymmetrical bis-pyrazolone couplers are those having the above general formula in which R is a methoxy phenyl group especially a p-methoxy phenyl group inasmuch as the reactivity of such couplers is great.

Representative unsymmetrical bis-pyrazolone couplers contemplated by my invention for particular use in photographic emulsions and color developers are prepared as follows:

EXAMPLE I v trichlorophenyl) -3 [3 "(2",4"-di-t.amylphenoxyacetamido)benzamido] 5 pyrazolonyl) }1- phenyl-3-methyl-4- (p-methoxybenzyl) -5-pyrazolone Enos-O 0 omo ONH- l l B 0 wherein R represents an aryl group of the benzene series such as phenyl, or phenyl substituted with alkoxy, alkyl, halogen, and so forth; for example, 3-methoxy-4-hydroxy-, 3,5-dimethoxy-4-hydroxy-, 4-chloro-, 2-chloro-,

O CH:

1 phenyl 3 methyl 4(4' methoxybenzylidene)- 5-pyrazolone was prepared by heating at C. for about one hour equal molecular proportions of p-methoxybenzaldehyde and 1-phenyl-3-methyl-5-pyrazolone in glacial acetic acid, dissolving the product in ethyl alcohol and crystallizing it therefrom. 1-(2',4',6'-trichlorophenyl) 3 [3"(2',4"-di-t.-amylphenoxy acetamido)lbenzamido-S-pyrazolone was prepared by acylation of 1-(2',4,6'-trichlorophenyl)-3-amino5-pyrazolone with mnitrobenzoyl chloride followed by reduction of the nitro group of the amide and acylation of the resulting amino group with 2,4-di-t.-amylphenoxyacetyl chlo- H e.

The desired unsymmetrical bis-pyrazolone was obtained from this benzylidene derivative as follows:

A mixture of 1.46 g. (.005 mole) 1-phenyl-3-methyl-4- (4'-methoxybenzylidene)S-pyrazolone and 3.4 g. (.005

mole) 1-(2,4',6-trichlorophenyl)-3-[3"(2",4-diamylsodium acetate. After refluxing for one hour, the mixphenoxyacetamido)benzamido]-5-pyrazolone was disture was poured into 200 cc. of water with stirring. The solved in 50 ml. of acetic acid containing 5 g. of sodium yellowish precipitate which resulted was collected and reacetate. The mixture was refluxed one hour and the crystallized from amixture of benzene and ligroin. There solution poured with stirring into 200 cc. of water. The 5 results a salmon-colored powder melting at 145-147. resulting precipitate was recrystallized from methanol Analysis.Calculated for C45H41O5N7S: C, 68.3; H, giving5 a cream-white crystalline powder melting at F, 12.4; S, 4.0. Found: C, 67.9; H, 4.9; N, 11.9; 152-1 4.

Analysis.Calculated for C52H5306N6Cl31 C, 64.8; H, When the compoundsil) and (II of Examples I and 5.5; N, 8.7; CI, 11.1. Found: C, 65.5; H, 5.5; N, 8.3; 11 above were dispersed in silver halide emulsions as cou- Cl, 10,8, plers, the dye images obtained on color development with EXAMPLE III {l-phenyl -3-aphenylbutyramido-S-pyraz0lonyl}1-4'(4"- tert.butylphen0xy)phenyl 3 [4"(4-tert.butylphenoxy phenyl] carbamyl-S-pyrazolone H H H C-C-C-C-C-NHGOOCzH ll l I 0 J 0:

l OCH:

EXAMPLE H p-phenylenediamine derivatives were examined spectrophotometrically and found to be a mean between the a{4((1' benzothiazolyl) 3[(3" tert.amylphen0xy)- images which were obtained from the two components benzamido] 5 pyrazol0nyl)}1 phenyl 3 aminocoated separately. The same result was obtained when 4(p-methoxybenzyl)-5-pyrazolone the color development reaction was carried out in solution: the spectrophotometric curve of the resulting dye O H was a mean between the curves of the two dyes obtained 5 from the separate parent components.

I 1 pheny1-3-a-phenylbutyramido-4-anisal-5-pyrazolone was prepared by acylation of 1-phenyl-3-amino-5-pyrazolone with oc-phenylbutyryl chloride, followed by reaction NH0 0- 0- N N=C with anisaldehyde as in Example I.

\ 1 [4(4-tert.butylphenoxy)phenyl] -3 [4(4""- tert.bu-

tylphenoxy)phenyl] carbamyI-S-pyrazolone was prepared c c 0. c-NH, by acylation of 4-tert.butylphenoxy aniline with 1(4' S g H l O 1 ll tert.butylphenoxy)phenyl-3-carboxy-5-pyrazolone.

The desired unsymmetrical bis-pyrazolone was obtained N as follows:

A mixture of 0.576 g. (.001 mole) of 1[4'(4"-tert.bu-

5 0 tylphenoxy) phenyl] -3 [4' 4""-tert.butylphenoxy)phen yl]carbamyl-S-pyrazolone, 0.44 g. (.001 mole) of l-phenyl-3-a-phenylbutyramido-4-anisal-5-pyrazolone, and 1 g.

of anhydrous sodium acetate in 10 ml. of glacial acetic acid was refluxed for 3 hours. The reaction mixture was poured into water. The resulting precipitate was col- 1-benzothiazoly1-3-[3-(tert.amylphenoxy)benzamido lected and recrystallized from equal parts of benzene and 4-p-methoxybenzylidenes-S-pyrazolone was prepared as P The resulting Product a cream White y the benzylidene derivative of Example I by reacting PQ meltmgat1207122 1 1 3- -5- l s Oxrdatrve coupling in solution with 3-methyl-4-aminoent 2,376,3 with 3-(tert.amylphenoxy)benzoyl chlodiethylaniline gave a magenta y of l Th8 ride and condensing the product with p-methoxybenzaldedye given by 1[4(4"-tert.butylphenoxy)phenyl]-3- hyde. The desired product was obtained therefrom as [4"(4""-tert.butylphenoxy)phenyl]carbamyl -5 pyrazofollows: lone alone has its primary maximum at 570 m l-phenyl- A mixture of 1.23 g. (.002 mole) of 1-benzothiazolyl- 3-a-phenylbutyramido-S-pyrazolone under the same con- 3[3-(tert.amylphenoxy)benzamido]-4-p-methoxybenzyli- U5) ditions gives a dye with its maximum absorption at dene-S-pyrazolone and 0.35 g. (.002 mole) 1-phenyl-3- 510 m A similar result was obtained when the bisamino-S-pyrazolone (U. S. Patent 2,376,380) was dispyrazolone was incorporated into a silver halide emulsolved in 50 cc. of glacial acetic acid containing 5 g. of sion and developed with the color developer.

EXAMPLE IV {1 (2-benz0thiaz0lyl) -36 [4(3"-p-tert.amylphen0xy)- benzamidophenylvaleramidol -5-pyraz0l0nyl}-1-phenylbutyrylamin0-4-p-methoxybenzal-S-pyrazolone S A O 1(2-benzotl1iazolyl) -3-5- [4'-(3"-p-tert.amylphenoxy)- benzamido]phenylvaleramido-S-pyrazolone was prepared by acylating 1(2-benz0thiazolyl)-3-amino-5-pyrazolone with 6-4-(3'-p-tert.amylphenoxy)benzamidophenyl valeryl chloride.

The desired bis-pyrazolone was prepared as follows:

A mixture of 1.35 g. (.002 mole) of l(2'-benzothiazolyl) 3 6 [4 (3" p tert. amylphenoxy)benzamido]phenylvaleramido-S-pyrazolone and 0.88 g. (.002 mole) of 1-phenyl-3-a-phenylbutyramido-4-anisylidene-5- pyrazolone (Example III) in 20 ml. of glacial acetic acid containing 1.5 g. anhydrous sodium acetate was heated at reflux for 3 hours. The reaction mixture was poured into water. The brownish precipitate was collected by suction filtration and recrystallized from methyl alcohol. There resulted a cream-white powder, M. P. 150-152".

On oxidative coupling with 3-methyl-4-aminodiethylaniline in solution a dye of k z530 my (in n-butyl acetate) was produced. Chromatographic analysis showed the dye to consist of two distinct components with A at 524 m, and 542 III u, respectively.

A similar result was obtained when the coupler was used in an emulsion layer and developed with the colorforming developer.

In the manner of the above examples, other aldehydes such as benzaldehyde, p-dimethylamino-, p-chloro-, ochloro-, p-nitro-, p-hydroxy benzaldehydes, syringaldehyde, vanillaldehyde, etc., may be reacted with a 5- pyrazolone, fusing the compounds together when required, and the resulting benzylidene compound further reacted with a different pyrazolone to obtain unsymmetrical bispyrazolones contemplated by my invention.

The coupler compounds of the invention are designed primarily for use in silver halide emulsions and to this end may be incorporated in emulsions by the methods of Mannes et al. U. S. Patents 2,304,939 and 2,304,940, granted December 15, 1942, and Jelley et al. U. S. Patent 2,322,027, granted June 15, 1943. In the process of the latter patent, the coupler is dissolved in a water-insoluble material such as dimethyl phthalate and the solution is then dispersed in the sensitive emulsion. The couplers may be in emulsion layers of gelatin or other waterpermeable colloidal carriers, such as albumin, collodion, organic esters of cellulose, or synthetic resins. The emulsion may be supported by transparent medium such as glass, a cellulose ester or synthetic resin or a nontransparent medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer or as superposed layers on one or both sides of the support. The emulsion layers may be differently sensitized, the emulsions containing the couplers of the invention forming magenta images, preferably, but not necessarily, being sensitized primarily to green light.

A typical color developer for use in developing emulsion layers containing the coupler compounds of the invention is as follows:

Grams Z-amino-S-diethylamino toluene sulfate 2.5 Sodium sulfite (anhydrous) 5 Sodium carbonate (anhydrous) 20 Potassium bromide 2 Water to 1,000 cc.

While the unsymmetrical bis-pyrazolones of the invention are primarily intended for use in emulsion layers, they can be used in color-developing compositions such as given above. The couplers are incorporated into the developer compositions by first dissolving in a solvent such as isopropyl alcohol and this solution is then added to the alkaline developer composition. About 3 grams of coupler are suitable for use in developer compositions such as the above.

What I claim is:

1. A photographic silver halide emulsion containing as a coupler compound a member of the class consisting of a{4{1(2,4',6, trichlorophenyl)-3 [3"(2",4-di-t.arnylphenoxyacetamido)benzarnido] 5 pyrazolonyl}}1- phenyl 3 methyl 4 (p methoxybenzyl) 5 pyrazolone, u{4{(1' benzothiazolyl) 3'[(3" tert.amylphenoxy) benzamido] 5 pyrazolonyl}}1 phenyl 3 amino 4(p methoxybenzyl) 5 pyrazolone, {1- phenyl 3 a phenylbutyramido 5 pyrazolonyl}1,4- (4 tert.butylphenoxy)phenyl 3 [4(4' tert.butylphenoxy)phenyllcarbamyl 5 pyrazolone and {1(2- benzothiazolyl) 3 6 [4'(3 p tert.amylphenoxy)- benzamidophenylvaleramido] 5 pyrazolonyl} lphenyl 3 oz phenylbutyrylamino 4 p methoxybenzal-S-pyrazolone.

2. A photographic silver halide emulsion containing as a coupler compound: a{4{l(2',4',6', trichlorophenyl)- 3 [3"(2",4" di t.amylphenoxyacetamido)benzamido] 5 pyrazolony1}}l phenyl 3 methyl 4 (p methoxybenzyl) -5-pyrazolone.

3. A photographic silver halide emulsion containing as a coupler compound: a{4{(l-benzothiazolyl)-3'[(3" tert.- amylphenoxy)benzamido] 5 pyrazolonyl}}1 phenyl- 3 amino 4(p methoxybenzyl) 5 pyrazolone.

4. A photographic silver halide emulsion containing as a coupler compound: {1-phenyl-3-a-phenylbutyramido-5- pyrazolonyl}l,4(4 tert.butylphenoxy)phenyl 3 [4"- 4'"-tert.butylpl1enoxy) phenyl] carbamyl-5-pyraz 1one;-

5. A photographic silver halide emulsion containing as a coupler compound: {l(2'-benzothiazo1yl)-3-5-[4'(3"- p tert.amylphenoxy)benzamidophenylvaleramido] 5- pyrazolonyl} 1 phenyl 3 0c phenylbutyrylamino 4- p-rnethoxybenzal-S-pyrazolone.

References Cited in the file of this patent UNITED STATES PATENTS 2,213,986 Kendall et a1 Sept. 10, 1940 2,294,909 Jennings Sept. 8, 1942 2,411,951 Bavley Dec. 3, 1946 2,435,550 Bavley Feb. 3, 1948 OTHER REFERENCES Vittum et al.: Abstract in vol. 631, page 283 of the Ofiicial Gazette, February 7, 1950. 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COUPLER COMPOUND A MEMBER OF THE CALSS CONSISTING OF A(4(1(2'',4'',6'', TRICHLOROPHENYL)-3(3"(2"'',4"''-DI-T.AMYLPHENOXYACETAMIDO)BENZAMIDO) - 5 - PYRAZOLONYL))1PHENYL - 3 - METHYL - 4 - (P -METHOXYBENZYL) - 5 -PYRAZOLONE, A(4((1'' - BENZOTHIAZOLYL) - 3''((3" TERT.AMYLPHENOXY) - BENZAMIDO) - 5 - PYRAZOLONYL))1 - PHENYL - 3 AMION - 4(P - METHOXYBENZYL) - 5 - PYRAZOLONE, (1 PHENYL - 3 -A-PHENYLBUTYRAMIDO - 5 - PYRAZOLONE, (1(4 "-TERT. PHENYLPHENOXY)PHENYL - 3 - (4"''(4"''-TERT.BUTYLPHENOXY)PHENYL)CARBAMYL - 5 - PYRAZOLONE AND (1(2''BENZOTHIAZOLYL) - 3 - 8 - (4''(3" - P-TERT.AMYLPHENOXY)BENZAMIDOPHENYLVALERAMIDO) - 5 - PRYAZOLONYL) - 1PHENYL - 3 - A - PHENYLBUTYRYLAMINO - 4 - P - METHOXYBENZAL-5-PYRAZOLONE. 